US 12,281,058 B2
Manganese catalysts and their use in hydrogenation of ketones
Magnus Widegren, Fife (GB); and Matthew Lee Clarke, Fife (GB)
Assigned to UNIVERSITY COURT OF THE UNIVERSITY OF ST ANDREWS, Fife (GB)
Appl. No. 17/421,251
Filed by University Court of the University of St Andrews, Fife (GB)
PCT Filed Jan. 8, 2020, PCT No. PCT/GB2020/050035
§ 371(c)(1), (2) Date Jul. 7, 2021,
PCT Pub. No. WO2020/144476, PCT Pub. Date Jul. 16, 2020.
Claims priority of application No. 1900253 (GB), filed on Jan. 8, 2019.
Prior Publication US 2022/0119329 A1, Apr. 21, 2022
This patent is subject to a terminal disclaimer.
Int. Cl. C07C 29/156 (2006.01); B01J 31/18 (2006.01); C07F 17/02 (2006.01)
CPC C07C 29/156 (2013.01) [B01J 31/1815 (2013.01); B01J 31/189 (2013.01); C07F 17/02 (2013.01); B01J 2231/643 (2013.01); B01J 2531/0205 (2013.01); B01J 2531/72 (2013.01); B01J 2531/842 (2013.01)] 20 Claims
 
1. A method comprising hydrogenating a ketone in the presence of (i) a base, (ii) hydrogen gas and (iii) a catalyst comprising a charged or neutral complex of formula (I):

OG Complex Work Unit Chemistry
wherein:
Mn is a manganese atom or a manganese ion in oxidation state (I) to (VII);
R1 and R2 are each independently C4-8monocyclic aryl or C3-7monocyclic heteroaryl moieties, optionally substituted one or more times with a first electron donating group;
-Fc- denotes a ferrocene (bis(η5-cyclopentadienyl)iron) moiety covalently bonded via adjacent carbon atoms of one of the two cyclopentadienyl moieties, and which may be optionally further substituted, in either cyclopentadienyl ring, one or more times with a substituent selected from the group consisting of halo, aliphatic C1-6hydrocarbyl, trihalomethyl, aryl, heteroaryl, hydroxy, nitro, amino, alkoxy, alkylthio, carboxylate, sulfonate, phosphate, cyano, thio, formyl, ester, acyl, thioacyl, carbamido and sulfonamido;
—Z— is an alkylene linker of the formula —(CH2)1-6— in which one or more of the hydrogen atoms of the alkylene may be independently substituted with an alkyl, aryl, heteroaryl, hydroxy, nitro, amino, alkoxy, alkylthio or thiol substituent;
—Nx is a nitrogen-containing heteroaryl moiety, optionally substituted one or more times with a second electron donating group, with the proviso that at least one of R1, R2 and —Nx is substituted one or more times with the first and/or second electron donating group respectively; and
L1-L3 constitute one, two or three ligands in which each of L1-L3 independently represents a monodentate neutral or anionic ligand; or one of L1-L3 represents a monodentate neutral or anionic ligand and the other two of L1-L3 together represent a bidentate neutral or anionic ligand; or L1-L3 together represent a tridentate neutral or anionic ligand,
wherein, when the complex of formula (I) is charged, the catalyst comprises one or more additional counterions to balance the charge of the complex.